COPOLYMERES AVEC SEQUENCE DE SILICONE, RETICULABLES AUX UV

UV CURABLE SILICONE BLOCK COLPOLYMERS

Abrégé anglais

UV CURABLE SILICONE BLOCK COPOLYMERS
Abstract
There are provided curable polysiloxane block
copolymers having at least one block of diorganosiloxane
units, at least one block of trifunctional arylsiloxane
units, optionally, at least one block of trifunctional
alkylsiloxane units, and at least one block of acrylate-
functional siloxane units. The cured compositions are
transparent, self-bonding, tough, dirt repellent and
solvent resistant. Methods for making the block
copolymers, curable compositions, and articles of
manufacture are also provided.

Revendications

- 19 -
The embodiments of the invention in which an
exclusive property or privilege is claimed are defined
as follows:
1. A silicone block copolymer composition,
comprising:
(a) at least one block consisting essentially of
from about 6 to about 120 units of the formula
<IMG>
(b) at least one block consisting essentially
of from about 3 to about 160 units of the formula
<IMG>
(c) at least one block consisting essentially
of from about 0.1 to about 20 mole percent of (a) and
(b) of units of the formula
<IMG>
where R is an independently selected alkyl radical
having 1 to 5 carbon atoms, aryl radical having 6 to 10
carbon atoms, or aralkyl radical having 6 to 10 carbon
atoms; R1 is an aryl or aralkyl radical having 6 to 10
carbon atoms; and R3 is an acrylic-functional radical
having the general formula
<IMG>
where the R4 radicals are the same or different and
represent hydrogen atoms or monovalent substituted or
unsubstituted hydrocarbon radicals having from 1 to 12
carbon atoms and R5 is a divalent substituted or unsub-
stituted hydrocarbon radical having from 2 to 12 carbon
atoms.

- 20 -
2. The composition of claim 1, further comprising
at least one block consisting essentially of from 1 to
about 80 units of the formula
<IMG>
where R is an alkyl radical having from 1 to 5 carbon
atoms.
3. The composition of claim 1 wherein siloxane
block (a) consists essentially of from about 6 to about
50 units, siloxane block (b) consists essentially of from
about 4 to about 75 units, and siloxane block (c) consists
essentially of from about 0.5 to about 10 mole percent of
the sum of said (a) blocks and (b) blocks.
4. The composition of claim 2 wherein there
is present from 1 to about 8 units of the formula
<IMG>
where R2 is an alkyl radical having from 1 to 5 carbon
atoms.
5. The composition of claim 1 wherein R3 is
acryloxypropyl, methacryloxypropyl or a mixture thereof.
6. A method for making a silicone block
copolymer composition, comprising:
(a) mixing an organic solvent, water and a
silanol terminated polydiorganosilosiloxane having
repeating units of from about 6 to about 120,
(b) adding to the reaction mass of step (a) an
amount of aryltrichlorosilane and acrylic-functional
dichlorosilane , and
(c) reacting the silanol terminated polydiorgano-
siloxane of step (a) with the chlorosilanes of step (b).
7. The method of claim 6 further comprising
adding in step (b) an amount of alkyltrichlorosilane.

- 21 -
8. The method of claim 6 wherein the aryl-
trichlorosilane and acrylic-functional dichlorosilane
are added to the reaction mass of step (a) simultaneously.
9. The method of claim 6 wherein the
aryltrichlorosilane and acrylic-functional dichlorosilane
are added to the reaction mass of step (a) consecutively.
10. The method of claim 6 wherein reaction
of the silanol terminated polydiorganosiloxane and the
chlorosilanes is effected by stirring at from about
25°C to about 50°C for from about 15 minutes to about
10 hours.
11. A curable composition, comprising
(A) 100 parts by weight of an organopolysiloxane
block copolymer, comprising:
(i) at least one block consisting essentially
of from about 6 to about 120 units of the formula
<IMG>
(ii) at least one block consisting essentially
of from about 3 to about in units of the formula
<IMG>
(iii) at least one block consisting essentially
of from about 0.1 to about 20 mole percent of
(a) and (b) of units of the formula
<IMG>
where R is an independently selected alkyl radical having
1 to 5 carbon atoms, aryl radical having 6 to 10 carbon
atoms, or aralkyl radical having 6 to 10 carbon atoms,
R1 is an aryl or aralkyl radical having 6 to 10 carbon
atoms; and R3 is an acrylic-functional radical having the
general formula

- 22 -
<IMG>
where the R4 radicals are the same or different and
represent hydrogen atoms or monovalent substituted or
unsubstituted hydrocarbon radicals having from 1 to 12
carbon atoms and R5 is a divalent substituted or unsub-
stituted hydrocarbon radical having from 2 to 12 carbon
atoms; and
(B) an amount of cure-initiator effective for
promoting crosslinking of said organopolysiloxane block
copolymer.
12. The composition of claim 11 wherein the
block copolymer further comprises at least one block
consisting essentially of from 1 to 80 units of the
formula
<IMG>
where R2 is an alkyl radical having from 1 to 5 carbon
atoms.
13. The composition of claim 11 wherein
siloxane block (A)(i) consists essentially of from
about 6 to about 60 units, siloxane block (A)(ii)
consists essentially of from about 4 to about 75 units,
and siloxane block (A)(iii) consists essentially of from
about 0.5 to about 10 mole percent of the sum of said
(A)(i) blocks and (A)(ii) blocks.
14. The composition of claim 12 wherein there
is present from 1 to about 8 units of the formula
<IMG>
where R2 is an alkyl radical having from 1 to 5 carbon
atoms.
15. The composition of claim 11 wherein R3
is acryloxypropyl, methacryloxypropyl or a mixture
thereof.

- 23 -
16. The composition of claim 11 wherein the
cure-initiator is a photoinitiator and is present in an
amount of from about 0.05 percent by weight to about
5 percent by weight based on the weight of the acrylic-
functional block copolymer.
17. A method for making a curable composition,
comprising mixing:
(A) 100 parts by weight of an organopolysiloxane
block copolymer, comprising:
(i) at least one block consisting essentially
of from about 6 to about 120 units of the
formula
<IMG>
(ii) at least one block consisting
essentially of from about 3 to about 160
units of the formula
<IMG>
(iii) at least one block consisting
essentially of from about 0.1 to about 20
mole percent of (a) and (b) of -units of -the
formula
<IMG>
where R is an independently selected alkyl radical
having 1 to 5 carbon atoms, aryl radical having 6 to
10 carbon atoms, or aralkyl radical having 6 to 10
carbon atoms; R1 is an aryl or aralkyl radical having
6 to 10 carbon atoms; and R3 is an acrylic-functional
radical having the general formula
<IMG>

- 24 -
where the R4 radicals are the same or different and
represent hydrogen atoms or monovalent substituted or
unsubstituted hydrocarbon radicals having from 1 to 12
carbon atoms and R5 is a divalent substituted or
unsubstituted hydrocarbon radical having from 2 to 12
carbon atoms; and
(B) an amount of cure-initiator effective for
promoting crosslinking of said organopolysiloxane block
copolymer.
18. The method of claim 17 wherein the block
copolymer further comprises at least one block consisting
essentially of from 1 to 80 units of the formula
<IMG>
where R2 is an alkyl radical having from 1 to 5 carbon
atoms.
19. The method of claim 17 wherein siloxane
block (A)(i) consists essentially of from about 6 to
about 50 units, siloxane block (A)(ii) consists
essentially of from about 4 to about 75 units, and
siloxane block (A)(iii) consists essentially of from
about 0.5 to about 10 mole percent of the sum of said
(A)(i) blocks and (A)(ii) blocks.
20. The method of claim 18 wherein there is
present from 1 to about 8 units of the formula
<IMG>
where R2 is a alkyl radical having from 1 to 5 carbon
atoms.
21. The method of claim 17 wherein R3 is
acryloxy propyl, methacryloxypropyl or a mixture thereof.
22. The method of claim 17 wherein the cure-
initiator is a photoinitiator and is present in an amount
of from about 0.05 percent by weight to about 5 percent

- 25 -
by weight based on the weight of the acrylic-functional
block copolymer.
23. A method for making an article of
manufacture, comprising:
(I.) applying to a substrate a curable
composition comprising:
(A) 100 parts by weight of an organopolysiloxane
block copolymer, comprising:
(i) at least one block consisting essentially
of from about 6 to about 120 units of the
formula
<IMG>
(ii) at least one block consisting
essentially of from about 3 to about 160 units
of the formula
<IMG>
(iii) at least one block consisting essentially
from about 0.1 to about 20 mole percent of (a)
and (b) of units of the formula
<IMG>
where R is an independently selected alkyl radical.
having 1 to 5 carbon atoms, aryl radical having 6 to
10 carbon atoms, or aralkyl radical having 6 to 10
carbon atoms; R1 is an aryl or aralkyl radical having
6 to 10 carbon atoms; and R3 is an acrylic-functional
radical having the general formula
<IMG>
where the R4 radicals are the same or different and
represent hydrogen atoms or monovalent substituted or

- 26 -
unsubstituted hydrocarbon radicals having from 1 to 12
carbon atoms and R5 is a divalent substituted or
unsubstituted hydrocarbon radical having from 2 to 12
carbon atoms; and
(B) an amount of cure-initiator effective for
promoting crosslinking of said organopolysiloxane block
copolymer;
(II.) curing said curable composition.
24. The method of claim 23 wherein the block
copolymer further comprises at least one block consisting
essentially of from 1 to 80 units of the formula
<IMG>
where R2 is an alkyl radical having from 1 to 5
carbon atoms.
25. The method of claim 23 wherein siloxane
block (A)(i) consists essentially of from about 6 to
about 50 units, siloxane block (A)(ii) consists essentially
of from about 4 to about 75 units, and siloxane block
(A)(iii) consists essentially of from about 0.5 to about
10 mole percent of the sum of said (A)(i) blocks and
(A)(ii) blocks.
26. The method of claim 24 wherein there is
present from 1 to about 8 units of the formula
<IMG>
where R2 is an alkyl radical having from 1 to 5 carbon
atoms.
27. The method of claim 23 wherein R3 is
acryloxypropyl, methacryloxypropyl or a mixture thereof.
28. The method of claim 23 wherein the
cure-initiator is a photoinitiator and is present in an
amount of from about 0.5 percent by weight to about 5
percent by weight based on the weight of the acrylic-
functional block copolymer.

- 27 -
29. The method of claim 23 wherein curing is
effected by exposing said curable composition to an amount
of ultraviolet radiation effective for curing said
composition.
30. The method of claim 23 wherein curing is
effected by heating said curable composition at an
elevated temperature for an amount of time effective for
curing said composition.
31. The method of claim 30 wherein said
elevated temperature is at least 100°C.
32. The method of claim 23 wherein the
substrate is an electronic component or device.
33. An article of manufacture prepared by a
process comprising the steps:
(I.) applying to a substrate a curable composition
comprising:
(Al 100 parts by weight of an organopolysiloxane
block copolymer, comprising:
(i) at least one block consisting essentially
of from about 6 to about 120 units of the
formula
<IMG>
(ii) at least one block consisting
essentially of from about 3 to about 160 units
of the formula
<IMG> and
(iii) at least one block consisting essentially
of from about 0.1 to about 20 mole percent of
(a) and (b) of unit of the formula
<IMG>

- 28 -
where R is an independently selected alkyl radical having
1 to 5 carbon atoms, aryl radical having 6 to 10 carbon
atoms, or aralkyl radical having 6 to 10 carbon atoms;
R1 is an aryl or aralkyl radical having 6 to 10 carbon
atoms; and R3 is an acrylic-functional radical having
the general formula
<IMG>
where the R4 radicals are the same or different and
represent hydrogen atoms or monovalent substituted
or unsubstituted hydrocarbon radicals having from 1
to 12 carbon atoms and R5 is a divalent substituted or
unsubstituted hydrocarbon radical having from 2 to 12
carbon atoms; and
(B) an amount of cure-initiator effective for
promoting crosslinking of said organopolysiloxane block
copolymer;
(II.) curing said curable composition.
34. The article of claim 33 wherein the block
copolymer further comprises at least one block consisting
essentially of from 1 to 80 units of the formula
<IMG>
where R2 is an alkyl radical having from 1 to 5 carbon
atoms.
35. The article of claim 33 wherein siloxane
block (A)(i) consists essentially of from about 6 to about
50 units, siloxane block (A)(ii) consists essentially of
from about 4 to about 75 units, and siloxane block (A)(iii)
consists essentially of from about 0.5 to about 10 mole
percent of the sum of said (A)(i) blocks and (A)(ii)
blocks.
36. The article of claim 34 wherein there is
present from 1 to about 8 units of the formula

- 29 -
<IMG>
where R2 is an alkyl radical having from 1 to 5 atoms.
37. The article of claim 33 wherein R3 is
acryloxypropyl, methacryloxypropyl or a mixture thereof.
38. The article of claim 33 wherein the cure-
initiator is a photoinitiator and is present in an amount
of from about 0.05 percent by weight to about 5 percent
by weight based on the weight of the acrylic-functional
block copolymer.
39. The article of claim 33 wherein curing is
effected by exposing said curable composition to an amount
of ultraviolet radiation effective for curing said
composition.
40. The article of claim 33 wherein curing
is effected by heating said curable composition at an
elevated temperature for an amount of time effective for
curing said composition.
41. The article of claim 40 wherein said
elevated temperature is at least 100°C.
42. The article of claim 33 wherein the
substrate is an electronic component or device.

Description

~L~
- l - 60SI 928
UV CURABLE 'SI'LICONE BDOC'K C'OPOLYMERS
Background of the Invention
The present invention relates to organosilicon
block copolymers and methods or making such block
copolymers. More particularly, the present inven-tion
relates to novel curable polysiloxane block copolymers having
at least one block of diorganosiloxane units, at least one
block of trifunctional aryl siloxane units, op-tionally,
at least one block of trifunctional alkyl siloxane units, and
at least one block of acrylate-functional siloxane units.
Random copolymers, although made from two or
more monomers which each have at least one desirable
property, do not have properties intermediate the
homopolymers. An example would be to copolymerize
monomer A which normally gives a hard and brittle film
with monomer B which normally gives a soft and flexible
film. The object of such copolymerization would be to
produce a copolymer having properties intermediate those
of homopolymers A and B, for example, to provide a
copolymer having a hard but flexible film. With random
copolymers it was Eound that the copolymer would generally
be brittle or would still be soft, and -the desired
intermediate properties woulcl not be obtained. Some
improvement might be realized such as the hard and
brittle polymer might be more flexible, but only
marginally so.
During the past few years a great deal of
in-terest has been shown in "sec~uential" or "block"

- 2 - 60SI 928
copolymers. Although the same mcnomers and percen-tages of
monomers make up the composition of the random copolymers
and the block copolymers, the final polymers in each case
diEfer widely in their properties. Thus, for example, a
block copolymer made of monomer A and monomer B may
provide the hard but flexible film which was not obtained
with the random copolymer.
It would be particularly desirable to obtain UV
curable block copolymers which result in -transparent,
adhesive, tough, dirt repellent and solvent resistant
compositions. Until the instant invention such
compositions were not available in the art.
U.S. Patent No. 2,793,223, issued May 21, 1957
to Merker, discloses acryloxymethylsiloxanes having
the formula
(CH = CRCOOCH2) (R )n Si 3-n
where R is hydrogen or methyl, R' is a monovalent
hydrocarbon radical, and n has a value from 1 to 2
inclusive. Such acryloxy substituted siloxanes can be0 copolymerized with siloxanes of the unit formula
R''m SiO4_m
where R" is a monovalent hydrocarbon radical, an
acetoxymethyl radical or a halogenated monovalent
hydrocarbon radical, and m has an average value from
1 to 3 inclusive. Consideration of the examples reveals
that random rather than block copolymers were prepared
and that only the toughness of -the resulting copolymers
is revealed.
Merker, in U.S. Patent No. 2,922,806, issued
30 January 26, 1960, expands upon the aforementioned
U.S. Patent No. 2,793,223 in that the acryloxy or
methacryloxy groups are attached -to silicon through a
divalent alkylene radical having from 2 to 4 carbon atoms.
Again, consideration of the examples does no-t disclose
that the resultant polymers or copolymers are adhesive,

7~
- 3 - 60SI 928
solvent resis-tant or dirt repellant.
Merker, U.S. Patent No. 2,956,044, issued
October 11, 1960, teaches that acryloxy-functional
polymers and copolymers prepared only from organosilicon
reactants are closely akin to conventional organosiloxane
polymers in their physical properties and hence are
useful as molding and impregnating resins, electrical
insulating varnishes, water repellent treatments,
lubricating fluids, and thermally resistant rubbers and
resins. However, by preparing copolymers of acrylate-
functional organosilicon units and organic vinylic units,
many of the properties of organic vinylic compounds can
be imparted to the copolymer, thereby making it useful as
a coating agent, impregnating and molding resin, adhesive
or bonding agent. Accordingly, the art is taught that
adhesion is imparted to UV curable acryloxy-functional
polysiloxanes by copolymerizing said polysiloxane with an
organic vinylic compound.
Ohto et al, U.S~ Patent No. 3,782,940,
issued ~anuary 1, 1974, discloses photopolymerizable
silicones containing at least one unit of the formula
Rl R2 (R4)
~ 3 ~ a
HC = C - C - R SiO or
" , 3-a-b
Xb 2
R R2 (R )m
HC = C - C - (R o) - SiO
" 1 , 3-m-n
O Xn 2
where Rl is hydrogen or an unsubstituted or haloyen-
substituted phenyl radical, R2 is hydrogen or a methyl
radical, R3 is an unsubstituted or halogen-substituted
divalent hydrocarbon radical having from 1 to 10 carbon
atoms, R4 is an unsubsti-tuted or halogen-substituted
monovalent hydrocarbon radical having from 1 to 10 carbon
atoms, X is a hydroxyl or alkoxyl radical having from 1

- 4 - 60SI~928
to 4 carbon atoms, a and b are each 0, 1 or 2 with the
proviso -that a+b=0, 1 or 2, 1 is 0 or 1, and m and n are
each 0, 1 or 2 with the proviso m+n=0, 1 or 2.
Ohto et all U.S. Patent No. 3,865,588, issued
February 11, 1975, teaches that the compositlons of the
aforementioned IJ.S. Patent Mo. 3,782,940 can be used in
planographic printing processes in addition to ion-
etching processes. Neither of the Ohto et al patents
disclose block copolymers which are transparent, adhesive,
tough, dirt repellent and solvent resis-tant.
Martin, U.S. Patent No. 3,878,263, issued
April 15, 1975, describes acrylate functional polysiloxane
polymers of the general formula
( R2 = C ~ - OR'' - SlO ~ (2SiO) (R~
wherein the R's may be the same or different and
represent hydrogen or monovalent hydrocarbon radicals
having from 1 to 12 carbon a-toms, R' is a monovalent
hydrocarbon radicals, a halogenated monovalent hydro-
carbon radical or a cyanoalkyl radical having from 1 to
lg carbon atoms, Rl' is a divalent hydrocarbon radical
having from 1 to 18 carbon atoms or the corresponding
divalent hydrocarbon radical having C-O-C linkages,
Rlll is a radical selected from the group consisting o~
R O0.5 and Rl3 sioo 5, Z is selected from the group
consisting of ORIlll, Rllll and OSiRl3, a and b equal
from 1 to 20,000, c equals from 0 to 3, and e equals from
0 to 2, however, when c is 0 than at least one Z must be
ORI I I I . Such polymers are sald to be useful as sizing
agents and as protective coatings for paper and fabrics.
Baney et al, U.S. Patent No. 4,035,355, issued
July 5, 1977, discloses that certain acrylate-containing

- 5 - 60SI 923
polyorganosiloxanes and a hydroperoxy polymerization
initiator result in an anaerobically curing sealant
composition.
The present invention is based on the discovery
that UV curable block copolymers having critical
amounts of specified siloxane blocks will result in
transparent, adhesive, tough, dirt repellent and solvent
resistant silicone compositions.
Summary of the Invention
It is an object of the present invention to pro-
vide novel ultraviolet light curable silicone compositions.
It is another object of the present invention
to provide transparent, self-bonding, tough, dirt
repellent and solvent resistant silicone compositions.
Still another object of the present invention is
to provide methods for making the aforesaid UV-curable and
UV-cured silicone compositions.
The stated objects are accomplished in one
aspect by a curable composition, comprising:
~A~ 100 parts by weight oE a polysiloxane
block copolymer, comprising:
~i~ a block having from about 6 to about
120 units of the formula
R
- sio -,
R
~iil a block having from about 3 to about
160 units of the formula
Rl
, 1.5
(iii~ optionally, a block having from 1 to
about 80 units of the formula
R2
; 30 - SiOl-5 , and
~.l
.

r3
- 6 - 60S~-928
(iv) from about 0.1 to about 20 mole
percent of (i), (ii) and (iii) of units of
the formula
,R3
-- sio --
where R is an independently selected alkyl radical having
1 to 5 carbon atoms, an aryl radical having 6 to 10 carbon
atoms, or an aralkyl radical having 6 to 10 carbon atoms;
Rl is an aryl or alkaryl radical having 6 to 10 carbon
atoms; R2 is an alkyl radical having 1 to 5 carbon atoms
and R3 is an acrylic-functional radical having the general
formula O
R C = C - C - O - R
R R
where the R4 radicals may be the same or different and
represent hydrogen atoms or monovalent substituted or
unsubstituted hydrocarbon radicals having from 1 to
12 carbon atoms, and R5 is a divalent substituted or
unsubstituted hydrocarbon radical having from 2 to 12
carbon atoms; and
(B) an amount of cure-initiator effective for
promoting crosslinking of said polysiloxane block
copolymer.
These and other objec-ts will become clear from
the following description taken together with the
accompanying claims.
Description of the Invention
In accordance with a first aspec-t of -the present
invention there is provided novel silicone block copolymers,
comprising:
(a) at least one block consisting essentially
of from about 6 to about 120 uni-ts of the formula
R
-- sio -- ,
R

~ 7 ~ 60SI 928
(b) at least one block consisting essentially
of from about 3 to about 160 units o~ the formula
Rl
,i1.5 '
(c) optionally, at least one block consisting
essentially of from 1 to about 80 units of the formula
R2
- SiOl-5 , and
~ d) at least one block consisting essentially
of from about 0.1 to about 20 mole percent of (a) and
(b~ of units of the formula
R3
-- SiO -
R
where R is an independently selected alkyl radical having
1 to 5 carbon atoms, an aryl radical having 6 to 10
carbon atoms or an aralkyl radical having 6 to lO carbon
: atoms; Rl is an aryl or aralkyl radical having 6 to 10
carbon atoms, R2 is an alkyl radical having 1 to 5 carbon
atoms and R3 is an acrylic-func-tional radical having the
general formula
R C = C - C - O - R5 -
R4 R4
where the R4 radicals may be the same or different and
represent hydrogen atoms or monovalent substituted or
unsubstituted hydrocarbon radicals having from 1 to 12
carbon atoms, and R5 is a divalent substituted or unsub-
stituted hydrocarbon radical having from 2 to 12 carbon
atoms.
component ~a) of the organopolysiloxane block
copolymer of the present invention may contain from about
6 to about 120 diorganopolysiloxane units, however, it
is preferred that each such block of diorganopolysiloxane

7~
- 8 - 60SI 928
units present in the block copolymer contain from about
6 to about 40 of such repea-ting diorganopolysiloxane
units. Most preferably there are present from about 12
to about 30 repeating diorganopolysiloxane units per
block.
The R radicals bonded to the sillcon atoms of
the diorganopolysiloxane block are lower alkyl radicals
or substituted alkyl radicals having from 1 to 5 carbon
atoms, aryl or alkaryl radicals having from 6 to lO carbon
atoms, or substituted aryl or alkaryl radicals of 6 to lO
carbon atoms. Examples of such radicals include methyl
ethyl, propyl, butyl, 3,3,3-trifluoropropyl,
B-cyanoethyl, phenyl, tolyl, chlorophenyl, bromophenyl
cyanophenyl and the like. Preferably, all of the organo
groups of the diorganopolysiloxane block are a mixture of
methyl groups and phenyl groups, and most preferably all
of the R groups are methyl radicals.
The diorganopolysiloxane blocks, especially
dimethylpolysiloxane blocks, will provide flexibility to
the cured composition in a manner analagous to the way
linear dimethylpolysiloxanes impart elasticity to silicone
sealants.
Component (b) of the organopolysiloxane block
copolymer of the present invention has from about 3 to
about 160 trifunctional aryl or alkary] units per block.
In the most preferred embodiment there are approximately
.75 to 1.5 trifunctional units of this type per diorgano-
siloxane unit (e.g. 4 to 75 units). Thus, for example,
if there are 18 dimethylsiloxane units in block (a),
there most preferably are from about 14 to about 27
trifunctional arylsiloxane units in block (b). Within a
broader aspect of -the present inven-tion, i-t is con-templated
that a less preferred ratio is from about 0.5 to about 2
trifunctional aryl or alkaryl units per diorganosiloxane
unit. In the broadest range, it is believed that there
can be from about O.] to about 5 trifunctional siloxane
units of this type per diorganosiloxane uni-t. The number

7~
- 9 - 6OSI 928
of such arylsiloxane units per block and -the number of
such arylsiloxane blocks will be dependent upon the
desired hardness or flexibility of the cured composition.
The Rl radicals bonded to the silicon atoms of
the trifunctional arylsiloxane block can have from 6 to
about 10 carbon atoms. Preferably, such radicals are not
substituted but in some instances the artisan may desire to
use, for example, halogen or cyano substituted aryl or
alkaryl radicals. Included within the scope of the Rl
radicals are, for example, phenyl, tolyl and xylyl, and halo
or cyano groups attached thereto in place of a hydrogen
atom. Most preferably all of the Rl groups are phenyl
radicals.
rrrifunctional arylsiloxane units wlthin the
scope of (b) impart hardness to the material in much
the same way a filler imparts tensile strength to a silicone
sealant. Consequently, it is not critical that a reinforc-
ing filler be included in the present composition.
Optional component (c) of the organopolysiloxane
block copolymer consists essentially of from 1 to 80
trifunctional alkylsiloxane units. Alkyl trifunctional
siloxy units are optional in the block copolymers of the
present invention, but their inclusion in block copolymers
provides particularly good compositions. Preferably such
trifunctional alkylsiloxane units are present at about 10
mole percent of the trifunctional arylsiloxane units,
however, they may be present from as little as about 5 mole
percent to as much as about 50 mole percent of the
arylsiloxane units. For example, if there are 18 dimethyl-
siloxane units and 14 to 27 trifunctional arylsiloxaneunits, there may be from 1 to about 14 alkylsiloxane units
present. More preferably there should be -two or three
alkylsiloxane units in the block.
rrhe R2 radicals of componen-t (c) are selected
from the alkyl R radicals as described hereinabove ~or
componen-t (a). The alkyl radicals of the trifunctional

~ r;
- 10 - 60SI 928
alkylsiloxane block need not be the same as the alkyl
radicals of the diorganosiloxane block. Most preferably
R is also methyl in these blocks.
Trifunctional alkylsiloxane units, like -the
trifunctional arylsiloxane units, also impart streng-th
and rigidity to the cured product.
Component Id~, an essential block oE the
copolymer, is present in an amount of from about 0.1
to about 20 mole percent of the sum of componen-ts (a)
and (b). More preferably the (d) units are present in
an amount ranging from about 0.5 to abou-t 10 mole percent
of components (a) and (b) and most preferably the (d)
units are present at about one mole percent of components
(a) and (b~. Thus, if there are 18 diorganosiloxane units,
18 trifunctional arylsiloxane units, and 3 trifunctional
alkylsiloxane units presen~, the copolymer can contain
from 1 to about 5 acrylic-containing diorganosiloxy units.
The R radicals of component (d) are selected from
the same R radicals described earlier for component (a).
It is not necessary that -these R groups be the same as
the other R groups but, preferably, all of the R groups
are methyl.
The R3 radicals of component (d) can be any
acrylic-functional radical of the general formula
R C = C - C - O - R5 -
R R
where the R4 radicals may be the same or differen-t and
represent hydrogen atoms or monovalent substituted or
unsubstituted hydrocarbon radicals having from 1 to 12
carbon atoms, and R5 is a divalent substi-tuted or
unsubstituted hydrocarbon radical having from 2 to 12
carbon atoms. Preferably, the R4 groups are all hydrogen,
methyl, or a mixture oE hydrogen and methyl. I-t is also
preferred that R5 be a divalent hydrocarbon group having
3 to 5 carbon atoms. Thus, the most preferred R3 radicals

- 11 - 60SI 928
are, for example, acryloxypropyl, methacryloxypropyl
and the like.
Acrylic-functional diorganosiloxane units within
the scope of component (d), in addition to providing sites
for crosslinking, also impart flexibility to the block
copolymer. Thus, component (d) enables the artisan to
simultaneously control both crosslink density and
flexibility. Of course, as the block copolymer is made
larger by including more than one block of each type,
the number of crosslinking sites will also increase
depending on the desired properties of the cured composition.
Monofunctional siloxane units and tetrafunctional
siloxane units can also be present in the block copolymers
of the present invention. These groups are not essential
to the instant invention but are not detrimental if present
in limited amounts. The amounts of such monofunctional
and tetrafunctional siloxane units which can be present
are readily determined by the artisan without undue
experimentation.
It will be apparent to those skilled in the art
that the block copolymers of the present invention are
not limited to those copolymers having equal numbers of
each type of block in the copolymer. Rather, the number
of each type of block can be varied depending upon whether
the cured composition is to be more rigid, and hence
requiring more trifunctional units, or more flexible, and
hence requiring more difunctional units. The artisan will
also appreciate that it is not critical that the blocks
be present in any particular sequence.
Those of ordinary skill in the art will further
appreciate that the degree of flexibility or riyidity can
also be controlled by the number of siloxane units in a
particular block. For example, if a more flexible
composition is desired, the artisan can increase the
length of the diorganopolysiloxane blocks. Of course,
the effect on the composition's flexibility will be
different depending upon whether the block length is

- 12 - 60SI 92~
increased or the number of diorganopolysiloxane blocks is
increased. Such variations as well as many others are
well within the skill of the artisan and are not intended
to limit the spirit or scope of the present invention.
It is permissible to dissolve the block
copolymers of the present invention in a suitab]e solvent,
for example, mineral spirits or toluene.
The block copolymers of the present invention
can be prepared by a variety of ways known in the art.
In a particularly preferred method 100 parts by weight of
a silanol terminated polydiorganosiloxane having repeating
units varying from 6 to 120 is placed in a reaction vessel
containing from about 100 -to 500 by weight or organic
solvent such as toluene and from about 500 to about 2500
parts by weight water. The amount of solvent and wa-ter
employed is not critical, and no advantage is found in
using excessively large quantities. Sufficient agitation
is applied to form a dispersion. An amount of phenyl-
trichlorosilane, methyltrichlorosilane and acrylic
functional dichlorosilane in a solvent such as toluene are
added to the reaction vessel containing the dispersion,
while providing sufficient agitation to maintain the
dispersion. The dispersion is stirred at from about
25C to about 50~C for anywhere from 15 minutes to 10
hours or more to effect reac-tion. The resultant aqueous
phase contains reaction by-produc-ts such as hydrogen chloride
while the organic phase contains the acrylic-functional
block copolymers of the present invention. If desired,
the block copolymers can be further purified by washing
wi-th water and then a~eotroping off residual water and
acid.
The amount of the respec-tive silanes added to
the initial dispersion can, of course, be varied as
described hereinabove to provide a block copolymer which
will impart to the cured composition the desired
properties. I-t is important that the addition of the

~ 2~ 3
- 13 - 60SI 928
reactants be kept in order -to produce the desired
copolymer where large blocks are to be prepared. Where,
however, the blocks are only of 1 or 2 repeating units t
all of the components can be mixed together. The artisan
will also be able to adapt other me-thods known in the art
to prepare the block copolymers of the present invention.
In a second aspect, the present invention provides
curable compositions which comprise -the hereinabove-
described block copolymers and at least one suitable
cure-initiator in an amount effecti~e for promoting cross-
linking of said block copolymer. Preferably there is
utilized an effective amoun-t of photoinitiator which
generally is from about 0.05 to 5~ by weight of the
acrylic-functional block copolymer, but can be more or
less depending upon the particular photoinitiator employed.
Examples of suitable photoinitiators include t-butyl-
perbenzoate, amino, nitro and phenol compounds such as
p-hydrodiphenyl, p-nitroaniline, 2,6-dichloro-4-nitro-
aniline, keto compounds such as acetophenone, Michler's
ketone, aldehydes such as benzaldehydes, quinones such
as benzoquinone and anthroquinone, and anthrone compounds
such as 3-methyl-1,3-diazo-1,9-benzanthrone. Other
photoinitiators suitable for use in the UV curable
composition of the invention can be ascertained by the
artisan without undue experimentation. Cure initiators
for heat curing are well known in -the art, for example,
benzoyl peroxide. Similarly, the artisan will know
suitable initiators such as Fenton's reagent for room
temperature curing.
The curable compositions of the present
invention can be prepared simply by mixing the cure
initiator into the block copolymer. It is possible,
of course, to include one or more optional ingredients
well known in the art such as inhibitors, fillers and
the like.
In a third aspect of the present inven-tion

- 14 - 60SI 928
there is provided a transparent, self-bonding, tough,
dirt repellent and solvent resistant composition.
Normally, the aforesaid curable composition of the
present invention is applied to a substrate, for example
an electronic component or device, and thereafter exposed
to an amount of ultraviolet radiation or heat (e.g. elevated
temperature or room temperature) effective for crosslinking
the block copolymer.
The particular details for curing the compositions
of the present invention will depend on the particular
application. ~Iowever, those skilled in the art will be
able to determine optimum curing conditions without
undue experimentation.
The following examples are illustrative of the
practice of the present invention and are not intended
to limit the scope of the claimed invention. All parts
are by weight unless o-therwise stated.
EXAMPLES
Example 1 - Preparation of Block Copolymers
-
Twenty five grams of silanol terminated
polydimethylsiloxane having 24 repeating units on
average per polymer chain, ninety grams of toluene and
500 grams of distilled water were placed into a three-
necked round bottom flask equipped with a thermometer,
a stirrer and a dropping funnel. Sufficient agitation
was applied to form a dispersion. In a predried flask
54 grams of phenyl-trichlorosilane, 3.8 grams of
methyltrichlorosilane, 5.0 grams of methacryloxypropyl-
methyldichlorosilane and 90 grams of toluene were admixed.
The chlorosilane admix-ture was then added to the
dispersion in the three-necked flask over a period of
about two minutes. Following addition of the chloro-
silanes, stirring was continued for about thirty
minutes at a temperature of about 45C. The aqueous
phase containing hydrogen chloride by-product was then
separated from the organic phase which contained
-the organopolysiloxane block copolymer. The organo-

15 - 60SI 928
polyslloxane layer was washed with wa-ter and azeotroped
for one hour to remove residual water and acid.
Additional examples were prepared wherein the amounts
of the various blocks was varied. The results are set
% forth in Table I.
f
.

- 16 - 60SI 928
~) N _ . ,1 rl
rl ~1 ~-1 rl N N -- O O
u~ ~ ~ ~ ~ ~ ~ ~ tn u~
a) o o o o ~ ~ rl
~ O ~D
,~ ~1 ~ ~1 ~ ~ 4~ 4
I~
~ O V
S~ O O
m m m m u~
N
,J
N
O o\ o\~ o~ o\o\ oP o\ o\ o\
~J ~ ~ ~ ~ ~ ~
o - ~ 3 3 3 3 3 3 3 3 3
N N N Ll') N .--1 ~I r-l ~1
~1
.,~1
O ~ ~
m~ ~ O .,U
E~ ~ O
~
~1 ~ ~) IYi ' N rl
41 0
~1 O ~0
r~
o o o o o o Q,
1~
rl N ~ g N a) ~ ,~
~ O ~ N O ~ I~ OC~ O10 0 n Ll~ ;:1 rl
m ,a),
,, m~ ~ o ~ o
N ~ N N N NN N N N tn C) (D
o\ (D a) a.
r~
a~ ~ O O o
~Ll ~I N ~) ~
~_ _ _ _

~ 17 - 60SI 928
Example 2-UV Cured Compositions Prepared from Block Copoly~er lg
To 100 parts by weight of the block copolymer
prepared in Example lg (dissolved in toluene) there was
added varying amounts of photoinitiator. The UV curable
composition was then applied to each of a glass plate,
epoxy plate and metal plate, the solvent evaporated,
and thereafter the coated substrate was exposed under a
nitrogen atmosphere to a UV source having an output of
420 watts for a time equivalent to 20 feet per minute.
The results are set forth in Table II.
TABLE II
Example # Photoinitiator~l) Result
2a 5 wt. % t-butylperbenzoa-te Tack-free cure
2b 3 wt. % t-butylperbenzoate Tack-free cure
15 2c 5 wt. % diethylacetophenone Tack-free cure
2d 4 wt~ % diethylacetophenone Tack--~ree cure
2e 3 wt. % die-thylacetophenone Tack-free cure
2f 2 wt. % diethylacetophenone Tack-free cure
2g 1 wt. % diethylacetophenone Tack-free cure
(1~ Based on the solids content of the block copolymer.
Each of the cure compositions was highly
transparent and exhibited excellent toughness, adhesion,
dirt repellency and solvent resistance.
Example 3 - Therma'l'ly'Cured Compositions Prepared
from Block Copolyme'r'la
Two curable compositions, identified as 3a and 3b,
were prepared by mixing 100 parts by weight of block
copolymer la with 1 part by weight Supersol PMS (50% butyl
peroctoate in mineral spirits). Two more curable
compositions, identified as 3c and 3d, were prepared by
mixing 100 parts by weight of block copolymer la with
1 part by weight benzoyl peroxide. Examples 3a and 3c
were placed in an oven maintained at 80C and Examples 3b
and 3d were placed in an oven main-tained at 100C.
The results are set forth in Table III.

- 18 - 60SI 928
_ABLE III
Example # Curing Tem-p. _uring Ti_e Result
3a 80C 10 min. No cure
3a 80C 20 min. No cure
3a 80C 30 min. No cure
3a 80C 40 min. No cure
3b 100C 5 min. No cure
3b 100C 10 min. Tack-free cure
3c 80C 10 min. No cure
3c 80C 20 min. No cure
3c 80C 25 min. No cure
3d 100C 5 min. No cure
3d 100C 10 min. Tack-free cure
Example 4 - Room Temperature Cure Compositions
Prepared from Block Copolymer la
One hundred parts by weight of block copolymer la
(dissolved in toluene) was mixed wi-th 3 par-ts cumene
hydroperoxide and 1 drop cobalt naph-thalate (Fen-ton's
reagent) as well as 1.5 par-ts -triethylamine accelerator.
The composition was cast on ylass, epoxy and metal
substrates. In each case, a brownish, transparent
composition having excellent adhesion, toughness, dirt
repellency and solvent resistance was obtained in about
ten minutes. Additional room temperature cured compositions
were prepared as set forth in Table IV~
TABLE IV
Block
Example # Copolymer Photoinitia-tor Metal Aci_ Resul-t
~a(l)20 parts 0.5 part 50 ppm 1.5 w-t% opaque( )
t-butylperbenzoate Ferric (2) id~2) Cure
~b(l)20 par-ts 0.5 part 50 ppm 1.5 w-t% opa~ue( )
benzyl Ferric (~) Male~2c) cure
peroxi.de Sulfate Acid
4c(l)20 par-ts 0.5 part 500 ppm 1.5 w-t% clear(3)
benzyl Iron (III) Me-tha- cure
peroxide 2.~- crylic Acid
pentanediona-te
(1) includes 3.3 parts Akrochem ~0 accelerator
(2) ferric sulfa-te and maleic a~id are insoluble in -toluene
(3) curing -took about three hours